2-phenoxyphenylacetic acid derivatives, method and intermediate products for the production thereof, their use, and agents containing the same for combating fungicidal pests

ABSTRACT

2-Phenoxyphenylacetic acid derivatives of the formula I                    
     where the substituents and the index have the following meanings: 
     A is                    
      where 
     R 1  is halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, CF 3 , C 1 -C 4 -haloalkoxy, formyl, C(═O)NR a R b  or C(R a )═NOR b ; 
     R a  is hydrogen or C 1 -C 4 -alkyl; 
     R b  is C 1 -C 4 -alkyl; 
     n is 1, 2, 3 or 4, where the groups R 1  may be different if n is not 1; 
     R 2  is halogen, CH 3  or CF 3 ; 
     m is 0 or 1; and 
     X is OCH 3  or NHCH 3 ; 
     processes and intermediates for preparing the compounds I and the use of the compounds I for controlling harmful fungi are described.

TECHNICAL FIELD

The present invention relates to 2-phenoxyphenylacetic acid derivativesof the formula I:

where the substituents and the index have the following meanings:

A is

 where

R¹ is halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, CF₃, C₁-C₄-haloalkoxy, formyl,C(═O)NR^(a)R^(b) or C(R^(a))═NOR^(b);

R^(a) is hydrogen or C₁-C₄-alkyl;

R^(b) is C₁-C₄-alkyl;

n is 1, 2, 3 or 4, where the groups R¹ may be different if n is not 1;

R² is halogen, CH₃ or CF₃;

m is 0 or 1; and

X is OCH₃ or NHCH₃.

In addition, the invention relates to processes and intermediates forpreparing the compounds I, and to the use of the compounds I forcontrolling harmful fungi.

BACKGROUND ART

2-Phenoxyphenylacetic esters are known from EP-A 253 213 and EP-A 254426, and the corresponding amides are described in 45 EP-A 398 692 andEP-A 477 631. The compounds described in the abovementioned publicationsare suitable for use as crop protection agents against harmful fungi.

However, in many instances their activity is unsatisfactory.

DISCLOSURE OF INVENTION

It is an object of the present invention to provide compounds havingimproved activity.

We have found that this object is achieved by the 2-phenoxyphenylaceticacid derivatives of the formula I. Furthermore, we have foundintermediates and processes for preparing the compounds I, and theiruse, and compositions comprising them for controlling harmful fungi.

The compounds of the formula I differ from the compounds known from theabovementioned publications in the specific variation of thesubstitution at the 2-phenoxy radical by a substituted phenyl ring inmeta- or para-position and, if appropriate, a further substituent inmeta- or para-position.

The compounds of the formula I can be obtained per se by the processesdescribed in EP-A 253 213, EP-A 254 426, EP-A 398 692 and EP-A 477 631.

MODE(S) FOR CARRYING OUT THE INVENTION

In particular, the compounds of the formula I are obtained by reactingalkyl α-phenyl-α-ketoacetates of the formula II under basic conditionswith phenols of the formula III to give alkylα-(2-phenoxyphenyl)-α-ketoacetates of the formula IV. In formula II, Lis a leaving group customary for nucleophilic aromatic substitution,such as halogen, in particular fluorine or chlorine, or sulfonate ornitro. This reaction is carried out under generally customaryconditions, similar to WO-A 97/24317.

Keto esters IV are reacted with O-methylhydroxylamine or its acidaddition salt of the formula Va, if appropriate in the presence of abase, under the conditions described in EP-A 493 711, to give oximeethers of the formula IA.

If X in the formula I is NHCH₃, the esters of the formula IA areconverted with methylamine according to methods known from EP-A 398 692into the amides of the formula IB.

In the formula Va, Q is the anion of an inorganic acid, in particular ahalide ion.

Phenols of the formula III are known from the literature, or they can beobtained by methods known from the literature [cf.: WO-A 96/23749; WO-A97/18188; JP-A 04/173756; JP-A 08/157406; EP-A 625 726; Synthesis(1990), 827-833].

Alternatively, the compounds of the formula I can also be obtained bythe method known from WO-A 95/34526.

In a further process, compounds of the formula I can also be preparedfrom compounds of the formula VI by transition-metal-catalyzed couplingwith a phenyl derivative of the formula VII.

In formula VII, M is an organometallic radical, such as, for example,B(OH)₂, Sn(CH₃)₃, Sn(n—C₄H₉)₃, Mg—Hal or Zn—Hal. In formulae VI and VII,“Hal” is a halogen atom, such as chlorine, bromine or iodine, inparticular bromine and iodine.

The reaction of VI with VII is generally carried out at 10° C.-150° C.,preferably at 50° C.-120° C., in an inert organic solvent [cf. WO-A98/11070; Synth. Commun. (1981), 513; Angew. Chem. Ind. Ed. (1986),508]. If M in the formula VII is B(OH)₂, the reaction is carried out inthe presence of a base [cf. Synth. Commun. (1981), 513; ibid (1994),709; J. Het. Chem. (1989), 865; J. Org. Chem. (1988), 2052; ibid (1994),6095].

Suitable solvents are ethers, such as dioxane, dimethoxyethane andtetrahydrofuran. It is also possible to use mixtures of theabovementioned solvents.

Bases which are suitable for the Suzuki reaction are, for example,potassium carbonate, sodium carbonate, sodium bicarbonate andtriethylamine.

Suitable catalysts are, for example:trans-bis(acetonitrile)palladium(II) chloride,bis(dibenzylideneacetone)palladium(0),bis(triphenylphosphine)palladium(II) chloride, palladium acetate,palladium chloride and tetrakis(triphenylphosphine)palladium(0).

The compounds of the formula VI are known from EP-A 253 213, EP-A 254426, EP-A 398 692 and EP-A 477 631, or they can be obtained by theroutes described in these publications.

If individual compounds I are not obtainable by the routes describedabove, they can be prepared by derivatization of other compounds I.

The reaction mixtures are worked up in a customary manner, for exampleby mixing with water, phase separation and, if required, chromatographicpurification of the crude products. Some of the intermediates and endproducts are obtained in the form of colorless or slightly brownish,viscous oils, which are purified or freed from volatile components underreduced pressure and at moderately elevated temperature. If theintermediates and end products are obtained as solids, purification canalso be carried out by recrystallization or digestion.

Owing to their C═N double bonds, the preparation of the compounds I mayyield E/Z isomer mixtures which can be separated into the individualcompounds in a customary manner, for example by crystallization orchromatography.

However, if the synthesis yields isomer mixtures, a separation isgenerally not necessarily required since in some cases the individualisomers can be converted into one another during the preparation for useor upon use (for example under the action of light, acids or bases).Similar conversions may also occur after use, for example in thetreatment of plants in the treated plant or in the harmful fungus to becontrolled.

With regard to the C═NOCH₃ double bond, preference, on account of theiractivity, is given to the E isomers of the compounds I (configurationbased on the OCH₃ group in relation to the COX group).

In the symbol definitions given in the formulae above, collective termswere used which generally represent the following substituents:

Halogen: fluorine, chlorine, bromine and iodine;

Alkyl: saturated, straight-chain or branched hydrocarbon radicals having1 to 4 carbon atoms, for example C₁-C₄-alkyl, such as methyl, ethyl,propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl and1,1-dimethylethyl;

Haloalkyl: straight-chain or branched alkyl groups having 1 to 4 carbonatoms (as mentioned above), where in these groups some or all of thehydrogen atoms may be replaced by halogen atoms as mentioned above, forexample C₁-C₂-haloalkyl, such as chloromethyl, bromomethyl,dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl,trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl,chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl,2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl,2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl,2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl;

Alkoxy: straight-chain or branched alkyl groups having 1 to 4 carbonatoms (as mentioned above) which are attached to the skeleton via anoxygen atom (—O—);

Haloalkoxy: straight-chain or branched haloalkyl groups having 1 to 4carbon atoms (as mentioned above) which are attached to the skeleton viaan oxygen atom (—O—);

Alkylamino: a straight-chain or branched alkyl group having 1 to 4carbon atoms (as mentioned above) which is attached to the skeleton viaan amino group (—NH—);

Dialkylamino: two straight-chain or branched alkyl groups which areindependent of one another and in each case have 1 to 4 carbon atoms (asmentioned above) which are attached to the skeleton via a nitrogen atom;

Alkoxycarbonyl: an alkoxy group having 1 to 4 carbon atoms (as mentionedabove) which is attached to the skeleton via a carbonyl group (—CO—);

Alkylaminocarbonyl: an alkylamino group having 1 to 4 carbon atoms (asmentioned above) which is attached to the skeleton via a carbonyl group(—CO—);

Dialkylaminocarbonyl: a dialkylamino group (as mentioned above) which isattached to the skeleton via a carbonyl group (—CO—).

With regard to the intended use of the 2-phenoxyphenylacetic acidderivatives of the formula I, particular preference is given to thefollowing meanings of the substituents, in each case on their own or incombination:

Particular preference is given to compounds IB.

Moreover, particular preference is given to compounds I in which theindex m is zero.

Likewise, particular preference is given to compounds I in which theindex n is 1 or 2.

In addition, particular preference is given to compounds I in which thegroup A is in position 3.

Particular preference is also given to compounds I in which R¹ ishalogen, C₁-C₄-alkoxy, CF₃, C₁-C₄-haloalkoxy, C₁-C₄-alkoxycarbonyl,C₁-C₄-alkylaminocarbonyl or di-(C₁-C₄-alkyl)aminocarbonyl.

Particular preference is also given to compounds I in which R¹ isfluorine, chlorine or CF₃.

Furthermore, preference is also given to compounds I in which R¹ is inposition 4.

In addition, preference is also given to compounds I in which two groupsR¹ are in the 2,4-position.

The particularly preferred embodiments of the intermediates of theformula IV with regard to the variables correspond to those of theradicals R¹, R² and A of the formula I.

The compounds I are suitable as fungicides. They have excellent activityagainst a broad spectrum of phytopathogenic fungi, in particular fromthe class of the Ascomycetes, Deuteromycetes, Phycomycetes andBasidiomycetes. Some of them act systemically and can be employed incrop protection as foliar- and soil-acting fungicides.

They are especially important for controlling a large number of fungi ina variety of crop plants such as wheat, rye, barley, oats, rice, maize,grass, bananas, cotton, soya, coffee, sugar cane, grape vines, fruitspecies, ornamentals and vegetable species such as cucumbers, beans,tomatoes, potatoes and cucurbits, and also in the seeds of these plants.

Specifically, they are suitable for controlling the following plantdiseases:

Alternaria species in vegetables and fruit,

Botrytis cinerea (gray mold) in strawberries, vegetables, ornamentalsand grape vines,

Cercospora arachidicola in groundnuts,

Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,

Erysiphe graminis (powdery mildew) in cereals,

Fusarium and Verticillium species in a variety of plants,

Helminthosporium species in cereals,

Mycosphaerella species in bananas and groundnuts,

Phytophthora infestans in potatoes and tomatoes,

Plasmopara viticola in grape vines,

Podosphaera leucotricha in apples,

Pseudocercosporella herpotrichoides in wheat and barley,

Pseudoperonospora species in hops and cucumbers,

Puccinia species in cereals,

Pyricularia oryzae in rice,

Rhizoctonia species in cotton, rice and lawns,

Septoria nodorum in wheat,

Uncinula necator in grape vines,

Ustilago species in cereals and sugar cane, and

Venturia species (scab) in apples and pears.

The compounds I are also suitable for controlling harmful fungi such asPaecilomyces variotii in the protection of materials (for example wood,paper, paint dispersions, fibers or fabrics) and in the protection ofstored products.

The compounds I are employed by treating the fungi or the plants, seeds,materials or the soil to be protected against fungal attack with afungicidally effective amount of the active compounds. The applicationmay be carried out before or after the infection of the materials,plants or seeds by the fungi.

The fungicidal compositions generally comprise from 0.1 to 95,preferably from 0.5 to 90%, by weight of active compound.

For use in crop protection, the application rates are, depending on thekind of effect desired, from 0.01 to 2.0 kg of active compound per ha.

The treatment of seeds generally requires active compound quantities offrom 0.001 to 0.1 g, preferably from 0.01 to 0.05 g, per kilogram ofseed.

For use in the protection of materials or stored products, the activecompound application rate depends on the kind of application area andeffect desired. Customary application rates in the protection ofmaterials are, for example, from 0.001 g to 2 kg, preferably from 0.005g to 1 kg, of active compound per cubic meter of treated material.

The compounds I can be converted into the customary formulations, e.g.solutions, emulsions, suspensions, dusts, powders, pastes and granules.The use form depends on the specific intended use; in any case, itshould ensure fine and uniform distribution of the compound according tothe invention.

The formulations are prepared in a known manner, e.g. by extending theactive compound with solvents and/or carriers, if desired usingemulsifiers and dispersants, it also being possible to use other organicsolvents as auxiliary solvents if water is used as the diluent. Suitableauxiliaries for this purpose are essentially: solvents such as aromatics(e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins(e.g. mineral oil fractions), alcohols (e.g. methanol, butanol), ketones(e.g. cyclohexanone), amines (e.g. ethanolamine, dimethylformamide) andwater; carriers such as ground natural minerals (e.g. kaolins, clays,talc, chalk) and ground synthetic minerals (e.g. finely divided silica,silicates); emulsifiers such as nonionic and anionic emulsifiers (e.g.polyoxyethylene fatty alcohol ethers, alkylsulfonates andarylsulfonates), and dispersants such as lignin-sulfite waste liquorsand methylcellulose.

Suitable surfactants are the alkali metal, alkaline earth metal andammonium salts of lignosulfonic acid, naphthalenesulfonic acid,phenolsulfonic acid and dibutylnaphthalenesulfonic acid,alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcoholsulfates and fatty acids and alkali metal salts and alkaline earth metalsalts thereof, salts of sulfated fatty alcohol glycol ethers,condensation products of sulfonated naphthalene and naphthalenederivatives with formaldehyde, condensation products of naphthalene orof naphthalene sulfonic acid with phenol and formaldehyde,polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol,octylphenol and nonylphenol, alkylphenol polyglycol ethers,tributylphenyl polyglycol ethers, alkylaryl polyether alcohols,isotridecyl alcohol, fatty alcohol ethylene oxide condensates,ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylatedpolyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitolesters, lignin-sulfite waste liquors and methylcellulose.

Suitable for preparing directly sprayable solutions, emulsions, pastesor oil dispersions are petroleum fractions having medium to high boilingpoints, such as kerosine or diesel fuel, furthermore coal-tar oils andoils of plant or animal origin, aliphatic, cyclic and aromatichydrocarbons, for example benzene, toluene, xylene, paraffin,tetrahydronaphthalene, alkylated naphthalenes or derivatives thereof,methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride,cyclohexanol, cyclohexanone, chlorobenzene, isophorone, strongly polarsolvents, for example dimethylformamide, dimethyl sulfoxide,N-methylpyrrolidone, and water.

Powders, compositions for broadcasting and dusts can be prepared bymixing or jointly grinding the active substances with a solid carrier.

Granules, for example coated granules, impregnated granules andhomogeneous granules, can be prepared by binding the active compounds tosolid carriers. Solid carriers are, for example, mineral earths, such assilica gel, silicas, silicates, talc, kaolin, attaclay, limestone, lime,chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate,magnesium sulfate, magnesium oxide, ground synthetic materials,fertilizers, such as ammonium sulfate, ammonium phosphate, ammoniumnitrate, ureas and products of vegetable origin, such as cereal meal,tree bark meal, wood meal and nutshell meal, cellulose powders and othersolid carriers.

The formulations generally comprise from 0.01 to 95% by weight,preferably from 0.1 to 90% by weight, of the active compound. The activecompounds are employed in a purity of from 90% to 100%, preferably from95% to 100% (according to the NMR spectrum).

Examples of formulations are:

I. 5 parts by weight of a compound according to the invention arethoroughly mixed with 95 parts by weight of finely divided kaolin. Thisaffords a dusting composition comprising 5% by weight of the activecompound.

II. 30 parts by weight of a compound according to the invention arethoroughly mixed with a mixture of 92 parts by weight of pulverulentsilica gel and 8 parts by weight of paraffin oil which had been sprayedonto the surface of this silica gel. This affords an active compoundpreparation having good adhesive properties (active compound content 23%by weight).

III. 10 parts by weight of a compound according to the invention aredissolved in a mixture comprising 90 parts by weight of xylene, 6 partsby weight of the addition product of 8 to 10 mol of ethylene oxide to 1mol of oleic acid N-monoethanolamide, 2 parts by weight of the calciumsalt of dodecylbenzenesulfonic acid and 2 parts by weight of theaddition product of 40 mol of ethylene oxide to 1 mol of castor oil(active compound content 9% by weight).

IV. 20 parts by weight of a compound according to the invention aredissolved in a mixture comprising 60 parts by weight of cyclohexanone,30 parts by weight of isobutanol, 5 parts by weight of the additionproduct of 7 mol of ethylene oxide to 1 mol of isooctylphenol and 5parts by weight of the addition product of 40 mol of ethylene oxide to 1mol of castor oil (active compound content 16% by weight).

V. 80 parts by weight of a compound according to the invention are mixedwell with 3 parts by weight of the sodium salt ofdiisobutylnaphthalene-alpha-sulfonic acid, 10 parts by weight of thesodium salt of a lignosulfonic acid from a sulfite waste liquor and 7parts by weight of pulverulent silica gel, and ground in a hammer mill(active compound content 80% by weight).

VI. 90 parts by weight of a compound according to the invention aremixed with 10 parts by weight of N-methyl-α-pyrrolidone, affording asolution which is suitable for use in the form of very small drops(active compound content 90% by weight).

VII. 20 parts by weight of a compound according to the invention aredissolved in a mixture comprising 40 parts by weight of cyclohexanone,30 parts by weight of isobutanol, 20 parts by weight of the additionproduct of 7 mol of ethylene oxide to 1 mol of isooctylphenol and 10parts by weight of the addition product of 40 mol of ethylene oxide to 1mol of castor oil. The solution is poured into 100,000 parts by weightof water and finely dispersed therein, affording an aqueous dispersioncomprising 0.02% by weight of the active compound.

VIII. 20 parts by weight of a compound according to the invention aremixed well with 3 parts by weight of the sodium salt ofdiisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of the sodiumsalt of a lignosulfonic acid from a sulfite waste liquor and 60 parts byweight of pulverulent silica gel, and ground in a hammer mill. Themixture is finely dispersed in 20,000 parts by weight of water,affording a spray liquor comprising 0.1% by weight of the activecompound.

The active compounds can be applied as such, in the form of theirformulations or in the application forms prepared therefrom, for examplein the form of directly sprayable solutions, powders, suspensions ordispersions, emulsions, oil dispersions, pastes, dusts, compositions forbroadcasting, or granules, by spraying, atomizing, dusting, broadcastingor watering. The application forms depend entirely on the intended uses;in any case, they should ensure very fine dispersion of the activecompounds according to the invention.

Aqueous use forms can be prepared from emulsion concentrates, pastes orwettable powders (spray powders, oil dispersions) by addition of water.To prepare emulsions, pastes or oil dispersions, the substances can behomogenized in water as such or dissolved in an oil or solvent, by meansof wetting agents, tackifiers, dispersants or emulsifiers. However,concentrates comprising active substance, wetting agent, tackifier,dispersant or emulsifier and possibly solvent or oil which are suitablefor dilution with water can also be prepared.

The active compound concentrations in the ready-to-use preparations canbe varied over a relatively wide range. In general, they are from 0.0001to 10%, preferably from 0.01 to 1%.

It is also possible to use the active compounds with good success in theultra-low-volume method (ULV), it being possible to apply formulationscomprising more than 95% by weight of active compound or even the activecompound without additives.

Oils of various types, herbicides, fungicides, other pesticides andbactericides can be added to the active compounds, if desired evenimmediately prior to application (tank mix). These agents can be addedto the compositions according to the invention in a weight ratio of 1:10to 10:1.

The compositions according to the invention in the use form asfungicides may also be present in combination with other activecompounds, for example with herbicides, insecticides, growth regulators,fungicides or else with fertilizers. In many cases, a mixture of thecompounds I, or of the compositions comprising them, in the use form asfungicides with other fungicides results in a broader fungicidalspectrum of activity.

The following list of fungicides in combination with which the compoundsaccording to the invention can be used is intended to illustrate thepossible combinations, but not to impose any limitation:

sulfur, dithiocarbamates and their derivatives, such as iron (III)dimethyldithiocarbamate, zinc dimethyldithiocarb-amate, zincethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate,manganese zinc ethylenediaminebisdithiocarbamate, tetramethylthiuramdisulfide, ammonia complex of zinc (N,N-ethylenebisdithiocarbamate),ammonia complex of zinc (N,N′-propylenebisdithiocarbamate), zinc(N,N′-propylenebisdithiocarbamate),N,N′-polypropylenebis(thiocarbamoyl)disulfide;

nitro derivatives, such as dinitro-(1-methylheptyl)phenyl crotonate,2-sec-butyl-4,6-dinitrophenyl-3,3-dimethyl acrylate,2-sec-butyl-4,6-dinitrophenylisopropyl carbonate, diisopropyl5-nitroisophthalate;

heterocyclic substances, such as 2-heptadecyl-2-imidazoline acetate,2,4-dichloro-6-(o-chloroanilino)-s-triazine, O,O-diethylphthalimidophosphonothioate,5-amino-1-[bis(dimethylamino)phosphinyl]-3-phenyl-1,2,4-triazole,2,3-dicyano-1,4-dithioanthraquinone,2-thio-1,3-dithiolo[4,5-b]quinoxaline, methyl1-(butylcarbamoyl)-2-benzimidazolecarbamate,2-methoxycarbonylaminobenzimidazole, 2-(furyl-(2))benzimidazole,2-(thiazolyl-(4))benzimidazole,N-(1,1,2,2-tetrachloroethylthio)tetrahydrophthalimide,N-trichloromethylthiotetrahydrophthalimide.N-trichloromethylthiophthalimide,

N-dichlorofluoromethylthio-N′,N′-dimethyl-N-phenylsulfuric diamide,5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole,2-thiocyanatomethylthiobenzothiazole, 1,4-dichloro-2,5-dimethoxybenzene,4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone, pyridine2-thio-1-oxide, 8-hydroxyquinoline or its copper salt,2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine,2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine-4,4-dioxide,2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide,2-methylfuran-3-carboxanilide, 2,5-dimethylfuran-3-carboxanilide,2,4,5-trimethylfuran-3-carboxanilide,N-cyclohexyl-2,5-dimethylfuran-3-carboxamide,N-cyclohexyl-N-methoxy-2,5-dimethylfuran-3-carboxamide,2-methylbenzanilide, 2-iodobenzanilide, N-formyl-N-morpholine2,2,2-trichloroethyl acetal,piperazine-1,4-diyl-bis-1-(2,2,2-trichloroethyl)formamide,1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloroethane,2,6-dimethyl-N-tridecylmorpholine or its salts,2,6-dimethyl-N-cyclododecylmorpholine or its salts,N-[3-(p-tert-butylphenyl)-2-methylpropyl]-cis-2,6-dimethylmorpholine,N-[3-(p-tert-butylphenyl)-2-methylpropyl]piperidine,1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-yl-ethyl]-1H-1,2,4-triazole,1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-ylethyl]-1H-1,2,4-triazole,N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N′-imidazolyl-urea,1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanone,1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanol,(2RS,3RS)-1-[3-(2-chlorophenyl)-2-(4-fluorophenyl)-oxiran-2-ylmethyl]-1H-1,2,4-triazole,α-(2-chlorophenyl)-α-(4-chlorophenyl)-5-pyrimidinemethanol,5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine,bis(p-chlorophenyl)-3-pyridinemethanol,1,2-bis(3-ethoxycarbonyl-2-thioureido)benzene,1,2-bis-(3-methoxycarbonyl-2-thioureido)benzene,

strobilurins, such as methylE-methoxyimino-[α-(o-tolyloxy)-o-tolyl]acetate, methylE-2-{2-[6-(2-cyanophenoxy)-pyridimin-4-yloxy]-phenyl}-3-methoxyacrylate, N-methyl E-methoxyimino-[α-(2-phenoxyphenyl)]acetamide,methyl-E-methoxyimino-[α-(2,5-dimethylphenoxy)-o-tolyl]acetamide,

anilinopyrimidines, such as N-(4,6-dimethylpyrimidin-2-yl)aniline,N-[4-methyl-6-(1-propynyl)pyrimidin-2-yl]aniline,N-(4-methyl-6-cyclopropylpyrimidin-2-yl)aniline,

phenylpyrroles, such as4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile,

cinnamides, such as3-(4-chlorophenyl)-3-(3,4-dimethoxyphenyl)acryloylmorpholine;

and a variety of fungicides, such as dodecylguanidine acetate,3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]glutarimide,hexachlorobenzene, methylN-(2,6-dimethylphenyl)-N-(2-furoyl)-DL-alaninate,DL-N-(2,6-dimethylphenyl)-N-(2′-methoxyacetyl)alanine methyl ester,N-(2,6-dimethylphenyl)-N-chloroacetyl-D,L-2-aminobutyrolactone,DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)alanine methyl ester,5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolidine,3-(3,5-dichlorophenyl)-5-methyl-5-methoxymethyl-1,3-oxazolidine-2,4-dione,3-(3,5-dichlorophenyl)-1-isopropyl carbamoylhydantoin,N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide,2-cyano-[N-(ethylaminocarbonyl)-2-methoximino]acetamide,1-[2-(2,4-dichlorophenyl)pentyl]-1H-1,2,4-triazole,2,4-difluoro-a-(1H-1,2,4-triazolyl-1-methyl)benzhydryl alcohol,N-(3-chloro-2,6-dinitro-4-trifluoromethylphenyl)-5-trifluoromethyl-3-chloro-2-aminopyridine,1-((bis-(4-fluorophenyl)methylsilyl)methyl-1H-1,2,4-triazole

SYNTHESIS EXAMPLES

The procedures given in the synthesis examples below were used to obtainfurther compounds I by appropriate modification of the startingmaterials. The compounds obtained in this manner are listed in thetables which follow, together with physical data.

Example 1 Preparation of Methyl[2-(3-Bromo-4-fluorophenoxy)phenyl]oxoacetate

A suspension of 3.75 g of 80% pure NaH in 50 ml of dimethyl sulfoxide(DMSO) was admixed with 21.7 g of 3-bromo-4-fluorophenol (cf. DE-A 19280 27) and then stirred at 20-25° C. for 30 min, and a solution of 22.7g of methyl 2-(2-fluorophenyl)oxoacetate in 100 ml of DMSO was addeddropwise. The reaction mixture was stirred at 20-25° C. forapproximately 12 hours, poured into ice-water and then extracted withethyl acetate. The organic phases were washed with 1 N aqueous sodiumhydroxide solution and water and dried, and the solvent was distilledoff, giving 35 g of the title compound.

¹H NMR (CDCl₃, ppm): δ=3.7 (3H); 6.7-8.0 (7H).

Example 2 Preparation of MethylE-[2-(3-Bromo-4-fluorophenoxy)phenyl]methoxyiminoacetate

A solution of 10.3 g of the keto ester from Example 1 in 100 ml ofmethanol was admixed with 3.7 g of O-methoxyamine hydrochloride andstirred at 20-25° C. for 30 hours. The solvent was removed and theresidue was then taken up in ethyl acetate, washed with water and thendried. The solvent was distilled off and the residue was chromatographedover silica gel (methyl tert-butyl ether [MtBE]/cyclohexane=9:1), giving4.4 g of the title compound and 1.9 g of the Z-isomer.

¹H NMR (CDCl₃, ppm): δ=3.8 (3H); 4.0 (3H); 6.8-7.5 (7H).

Example 3 Preparation of2-[2-(3-Bromo-4-fluorophenoxy)phenyl]-2-methoxyimino-N-methylacetamide

The solution of 4.4 g of the E-isomer from Example 3 in 80 ml oftetrahydrofuran was admixed with 8 g of 40% strength aqueous methylaminesolution and stirred at 20-25° C. for 3 hours. The mixture was thenpoured into water and extracted with ethyl acetate, and the ethylacetate phases were washed with water and then dried. Distillativeremoval of the solvent and silica gel chromatography(MtBE:cyclohexane=9:1) gave 3.9 g of the title compound.

¹H NMR (CDCl₃, ppm): δ=2.9 (3H); 3.9 (3H); 6.7 (1H); 6.9-7.5 (7H).

Example 4 Preparation of 2-[2-(6-Fluoro-4′-methylbiphenyl-3-yloxy)phenyl]-2-methoxyimino-N-methylacetamide

A solution of 0.3 g of the product from Example 3 in 15 ml ofdimethoxyethane was admixed with 0.2 g of 4-methylphenylboronic acid,0.17 g of sodium carbonate, 2 ml of water and 40 mg oftetrakis(triphenylphosphine)palladium(0) and refluxed for 20 hours. Themixture was then poured into water and extracted with ethyl acetate, andthe extract was washed with 1N aqueous sodium hydroxide solution andthen with water and dried. Distillative removal of the solvent andsilica gel chromatography (MtBE: cyclohexane=9:1) gave 0.3 g of thetitle compound.

¹H NMR (CDCl₃, ppm): δ=2.38 (3H); 2.9 (3H); 4.0 (3H); 6.8 (1H) 6.9-7.5(11H)

Example 5 Preparation of MethylE/Z-[2-(3-Iodophenoxy)phenyl]-methoxyiminoacetate

55 g of 3-iodophenol were added dropwise to a suspension of 6.9 g of 95%pure NaH in 50 ml of dimethyl sulfoxide (DMSO). The mixture was stirredat 25-33° C. for 30 min, after which a solution of 44.5 g of methyl2-(2-fluorophenyl)oxoacetate in 80 ml of DMSO was added dropwise. Thereaction mixture was stirred at 20-25° C. for approximately 48 hours andthen poured into ice-water and extracted with methyl tert-butyl ether(MtBE). The organic phases were washed with 1N aqueous sodium hydroxidesolution and water and dried and then freed from the solvent. Theresidue was taken up in 1 liter of methanol and admixed with 143 ml of a17.5% strength aqueous methoxyamine solution. The mixture was stirred at20-25° C. for 12 hours, after which the methanol was distilled off, theresidue was taken up in MtBE and water and the organic phases weredried. Removal of the solvent gave 58 g of the title compound as anE/Z-isomer mixture which was used without any further purification inExample 6.

Example 6 Preparation of MethylE-[2-(3-Iodophenoxy)phenyl]-methoxyiminoacetate

With ice-cooling, a solution of 75 g of the isomer mixture from Example5 in 350 ml of ethanol was saturated with hydrogen chloride and stirredat 20-25° C. for 12 hours. Distillative removal of the solvent andsilica gel chromatography (MtBE/cyclohexane=9:1) gave 48 g of pureE-isomer as a yellow oil.

¹H NMR (CDCl₃, ppm): δ=3.82 (3H); 4.0 (3H); 6.9-7.5 (8H).

Example 7 Preparation of2-[2-(3-Iodophenoxy)-phenyl]-2-methoxyimino-N-methylacetamide

A solution of 47 g of E-isomer from Example 6 in 180 ml oftetrahydrofuran was admixed with 80 g of 40% strength aqueousmethylamine solution and stirred at 20-25° C. for 2 hours. The mixturewas then poured into water and extracted with ethyl acetate, and theethyl acetate phases were washed with water and then dried. Distillativeremoval of the solvent and silica gel chromatography(MtBE:cyclohexane=9:1) gave 42.4 g of the title compound as a yellowoil.

¹H NMR (CDCl₃, ppm): δ=2.9 (3H); 3.9 (3H); 6.7 (1H); 6.9-7.4 (8H).

Example 8 Preparation of2-[2-(4′-Chlorobiphenyl-3-yloxy)phenyl]-2-methoxyimino-N-methylacetamide

A solution of 13 g of the product from Example 7 in 105 ml ofdimethoxyethane was admixed with 9.9 g of 4-chlorophenylboronic acid,6.7 g of sodium carbonate, 34 ml of water and 200 mg oftetrakis(triphenylphosphine)palladium(0) and refluxed for 3 hours. Themixture was then poured into water and extracted with ethyl acetate, andthe extract was washed with 1N aqueous sodium hydroxide solution andthen with water and dried. Distillative removal of the solvent andsilica gel chromatography (MtBE: cyclohexane=9:1) gave 9.5 g of productas colorless crystals of m.p. 118-121° C.

¹H NMR (CDCl₃, ppm): δ=2.9 (3H); 4.0 (3H); 6.7 (1H); 6.9-7.5 (12H).

Example 9 Preparation of MethylE/Z-[2-(4′-Chlorobiphenyl-3-yl-oxy)phenyl]methoxyiminoacetate

A solution of 5 g of 4′-chlorobiphenyl-3-ol (cf. WO 96/23749) in 40 mlof DMSO was added dropwise to a suspension of 0.68 g of 95% pure NaH in50 ml of dimethyl sulfoxide (DMSO). The mixture was stirred at 25-33° C.for 20 min, after which a solution of 4.4 g of methyl2-(2-fluorophenyl)oxoacetate in 30 ml of DMSO was added dropwise. Thereaction mixture was then stirred at 20-25° C. for 72 hours, poured intoice-water and extracted with methyl tert-butyl ether. The organic phaseswere washed with 1N aqueous sodium hydroxide solution and water anddried and then freed from the solvent. The residue was taken up in 1liter of methanol and admixed with 143 ml of a 17.5% strength aqueousmethoxyamine solution. The mixture was stirred at 20-25° C. for 12hours, after which the methanol was distilled off, the residue was takenup in MtBE and water and the organic phases were dried. Removal of thesolvent gave 4.0 g of the title compound as an E/Z-isomer mixture whichwas used without any further purification in Example 10.

Example 10 Preparation of MethylE-[2-(4′-Chlorobiphenyl-3-yl-oxy)phenyl]methoxyiminoacetate

With ice-cooling, the solution of 2.5 g of the isomer mixture fromExample 9 in 50 ml of methylene chloride was saturated with hydrogenchloride and stirred at 20-25° C. for 1 hour. Distillative removal ofthe solvent and silica gel chromatography (MtBE/cyclohexane=9:1) gave1.5 g of pure E-isomer as a yellow oil.

¹H NMR (CDCl₃, ppm): δ=3.8 (3H); 4.0 (3H).

TABLE I IB.1

Phys. data (m.p. [° C.]; IR [cm⁻¹]; No. (R¹)_(n) (R²)_(m) NMR [CDCl₃,ppm]) I-1 4-Cl H 128-130 I-2 4-CH₃ H 132-134 I-3 4-isopropyl H 135-137I-4 3-F H  85-88 I-5 4-Br H  56-59 I-6 2,4-Cl₂ H  98-100 I-7 4-CF₃ H112-114 I-8 2-F-4-CH₃ H 135-137 I-9 4-COCH₃ H 137-139 I-10 4-CHO H 57-60 I-11 2-OCH₃ H 144-146 I-12 4-tert.-butyl H 145-148 I-13 4-F H 87-90 I-14 3,5-Cl₂ H 149-152 I-15 3,5-(CF₃)₂ H 1675, 1380, 1280, 1172,1134 I-16 4-[C(CH₃)═NOCH₃] H  48-51 I-17 4-[CH═NOCH₃] H 1675, 1525,1480, 1233, 1054, 1041 I-18 3-Cl-4-F H 1674, 1478, 1237, 1040, 980 I-192-CH₃ H 110-113 I-20 3-CF₃ H  72-75 I-21 2-OCH₃ H 135-137 I-22 4-CH₃ 4-F2.38; 2.9; 4.0; 6.8; 6.9-7.5 I-23 4-F 4-F 2.9; 3.95; 6.8 I-24 4-Cl 4-F2.8; 4.0; 6.85

TABLE II IB.2

Phys. data (m.p. [° C.]; IR [cm⁻¹]; No. (R¹)_(n) (R²)_(m) NMR [CDCl₃,ppm]) II-1 4-F H 1668, 1242, 1032, 828 II-2 2-F H 1665, 1241, 1038, 980II-3 2-Cl H 1673, 1240, 1037, 976 II-4 3-Cl H 1671, 1241, 1038, 980, 786II-5 4-Cl H 1665, 1254, 1089, 1032, 823 II-6 3-F H 1670, 1241, 1038, 980

Examples of the Activity Against Harmful Fungi

The fungicidal activity of the compounds of the formula I wasdemonstrated by the following experiments:

The active compounds were prepared separately or jointly as a 10%strength emulsion in a mixture of 70% by weight of cyclohexanone, 20% byweight of Nekanil® LN (Lutensol® AP6, wetting agent having emulsifyingand dispersant action based on ethoxylated alkylphenols) and 10% byweight of Wettol® EM (nonionic emulsifier based on ethoxylated castoroil) and diluted with water to the desired concentration.

Use Example 1 Activity Against Powdery Mildew of Wheat

Leaves of potted weed seedlings c.v. “Fruhgold” were sprayed to runoffpoint with an aqueous active compound preparation which had beenprepared from a stock solution comprising 10% of active compound, 63% ofcyclohexanone and 27% of emulsifier, and, 24 hours after the spraycoating had dried on, dusted with spores of powdery mildew of wheat(Erysiphe graminis forma specialis tritici). The test plants weresubsequently placed in a greenhouse at from 20 to 24° C. and a relativeatmospheric humidity of from 60 to 90%. After 7 days, the extent ofmildew development was determined visually as % infection of the totalleaf area.

In this test, the plants which had been treated with 250 ppm of theactive compounds I-1 to I-8 and I-10 to I-24 showed an infection of atmost 5%, while the untreated plants showed an infection of 90%.

Use Example 2 Activity Against Plasmopara viticola

Leaves of potted grapevines cv. “Müller-Thurgau” were sprayed to runoffpoint with an aqueous active compound preparation which had beenprepared using a stock solution comprising 10% of active compound, 63%of cyclohexanone and 27% of emulsifier. To assess the persistency of thesubstances, the plants were kept for 7 days in a greenhouse after thespray coating had dried on. Only then were the leaves inoculated with anaqueous zoospore suspension of Plasmapara viticola. The grapevines werethen initially kept in a water vapor-saturated chamber at 24° C. for 48hours and then in a greenhouse at 20-30° C. for 5 days. After thisperiod of time, the plants were once more kept in a humid chamber for 16hours to promote sporangiophore eruption. The extent of the infection onthe undersides of the leaves was then determined visually.

In this test, the plants which had been treated with 16 ppm of theactive compounds I-1, I-2, I-4 to I-11, I-13, I-16 and I-18 to I-24showed an infection of at most 5%, while the untreated plants showed aninfection of 90%.

We claim:
 1. A 2-phenoxyphenylacetic acid compound of formula I:

where the substituents and the index have the following meanings: A is

 where R¹ is halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, CF₃, C₁-C₄-haloalkoxy,formyl, C(═O)NR^(a)R^(b) or C(R^(a))═NOR^(b); R^(a) is hydrogen orC₁-C₄-alkyl; R^(b) is C₁-C₄-alkyl; n is 1, 2, 3 or 4, where the groupsR¹ are identical or different if n is not 1; R² is halogen, CH₃ or CF₃;m is 0 or 1; and X is OCH₃ or NHCH₃.
 2. A process for preparing thecompound of formula I defined in claim 1, which comprises reacting amethyl α-phenyl-α-ketoacetate of formula II:

in which L is fluorine or chlorine under basic conditions with a phenolof formula III:

to give a methyl α-(2-phenoxyphenyl)-α-ketoacetate of formula IV:

reacting IV with O-methylhydroxylamine or its acid addition salt to givean oxime ether of formula IA:

and, if X in formula I is NHCH₃, converting the ester group of the etherof formula IA with methylamine to give an amide of formula IB:


3. The N-methyl-2-phenoxyphenylacetamide of formula I defined in claim1, wherein X is NHCH₃.
 4. The N-methyl-2-phenoxyphenylacetamide offormula I defined in claim 3, wherein A is bonded in 3-position relativeto the ether oxygen.
 5. The N-methyl-2-phenoxyphenylacetamide of formulaI defined in claim 4 wherein m is
 0. 6. A methylα-(2-phenoxyphenyl)-α-ketoacetate of formula IV:

wherein A is

 where R¹ is halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, CF₃, C₁-C₄-haloalkoxy,formyl, C(═O)NR^(a)R^(b) or C(R^(a))═NOR^(b); R^(a) is hydrogen orC₁-C₄-alkyl; R^(b) is C₁-C₄-alkyl; n is 1, 2, 3 or 4, where the groupsR¹ are identical or different if n is not 1; R² is halogen, CH₃ or CF₃;m is 0 or 1; and X is OCH₃ or NHCH₃.
 7. A composition suitable forcontrolling harmful fungi, comprising a solid or liquid carrier and thecompound of formula I defined in claim
 1. 8. A method of preparing thecomposition defined in claim 7 which comprises admixing the compound offormula I and at least one liquid or solid carrier.
 9. A method forcontrolling harmful fungi, which comprises treating the fungi ormaterials, plants, soil or seeds to be protected against fungal attackwith an effective amount of the compound of formula I defined in claim1.